Detergent-dispersant, additive composition for lubricant, and lubricant composition

ABSTRACT

Provided is a detergent-dispersant for a lubricant having excellent detergency and dispersibility effects. Specifically provided are: a detergent-dispersant including a heterocyclic compound having a heterocyclic skeleton derived from a compound selected from the group consisting of pyridines, pyrroles, pyrimidines, pyrazoles, pyridazines, imidazoles, pyrazines, triazines, triazoles, tetrazoles, oxazoles, oxadiazoles, thiazoles, thiadiazoles, furans, dioxanes, pyrans, and thiophenes; and an additive composition for a lubricant and a lubricant composition, each containing the detergent-dispersant.

TECHNICAL FIELD

The present invention relates to a detergent-dispersant and a lubricantcomposition containing the detergent-dispersant. More specifically, thepresent invention relates to an ashless detergent-dispersant, anadditive composition for a lubricant, and to a lubricant compositioncontaining the detergent-dispersant, which are excellent in hightemperature stability, high temperature detergency, and in basevalue-maintainable property, and has fine particle-dispersibility.

BACKGROUND ART

In general, as conventional ashless detergent-dispersants, there havebeen used a succinimide-based detergent-dispersant, ahydroxybenzylamine-based detergent-dispersant, and the like. With theirremarkable actions of dispersing fine particles being highly valued, theashless detergent-dispersants are extensively used as lubricantadditives for a gasoline engine oil, a diesel engine oil, a two-cycleengine oil, and the like. Further, those detergent-dispersants are eachregarded as one of very important additives for lubricants, because thedetergent-dispersants also have synergistic effects with zinc dialkyldithiophosphate or a metal-type detergent-dispersant. However, it hasoften been pointed out that the stability at high temperature and thedetergency at high temperature are insufficient.

In general, the conventional ashless detergent-dispersants including asuccinimide-based detergent-dispersant and a hydroxybenzylamine-baseddetergent-dispersant have been insufficient in detergency and stabilityat high temperature.

Examples of the application of a heterocyclic compound to a lubricantare described in the following patent documents.

In Patent Document 1, there is used benzotriazole as a corrosioninhibitor. Patent Document 2 describes an application of a triazolederivative to a refrigerator oil composition and makes a point in theeffect of abrasion resistance. In Patent Document 3, there is used animidazole fluorine derivative as a surface treating agent. PatentDocument 4 describes that polybenzoimidazole is used as a polymercontaining an internal lubricant. In Patent Document 5, there is adescription on a fluid composition for active suspension containingthiadiazole or benzotriazole and having excellent abrasion resistance.Patent Document 6 describes that a triazine derivative is used as adispersant for lubricants and fuels. In Patent Document 7, there is adescription on indazole thione additives for lubricants. In PatentDocument 8, there is a description on a fluid having low tractionproperty which has a triazine structure. Still further, in PatentDocument 9, there is a description on a lubricant composition includinga triazine derivative.

However, any of the above Patent documents neither describes each oftheir products as an ashless detergent-dispersant, nor does itparticularly make a point in a detergency of their products.

Patent Document 1: JP 01-29497 A

Patent Document 2: JP 06-100881 A

Patent Document 3: JP 06-157471 A

Patent Document 4: JP 07-506860 A

Patent Document 5: JP 08-165483 A

Patent Document 6: JP 2002-534436 A

Patent Document 7: JP 2003-505577 A

Patent Document 8: JP 2004-315703 A

Patent Document 9: JP 2004-331950 A

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

It is an object of the present invention to provide a heterocycliccompound useful as an ashless detergent-dispersant, an additivecomposition for a lubricant, and a lubricant composition containing thedetergent-dispersant which are excellent in high temperature stability,high temperature detergency, and in base value-maintainable property,and has excellent fine particle-dispersibility.

Means for Solving the Problem

In view of the above-mentioned circumstances of the prior art, theinventors of the present invention have conducted intensive studies inorder to develop a lubricant composition having improved detergency anddispersibility. As a result, the inventors have found that aheterocyclic compound having a specific chemical structure may exhibitexcellent properties as an ashless detergent-dispersant and may imparthigh temperature stability and the like to a lubricant for an internalcombustion engine and a transmission engine of a driving system. Thus,the present invention has been completed.

That is, the present invention provides the following Items (1) to (7) :

(1) A detergent-dispersant comprising a heterocyclic compound which isrepresented by the following general formula (I), and which may have adouble bond in a cyclic moiety:

where: X¹, X², X³, and X⁴ each independently represent “N” or “NH”, “O”,or “S”; “p” represents 0 or 1, “x” and “y” each independently representan integer of 0 to 2, “u” and “r” each independently represent aninteger of 0 to 4, “t” and “w” each independently represent an integerof 0 to 3, “v” represents an integer of 0 to 5 in a case where “p”represents 0 and “v” represents an integer of 0 to 3 in a case where “p”represents 1, “n” and “m” each independently represent an integer of 0to 3, “k” represents an integer of 0 to 3, and “x”, “y”, “n”, “m”, and“v” do not each represent 0 at the same time in a case where “p”represents 0; R¹ to R⁴ each independently represent a hydrogen atom or ahydrocarbon group which may have at least one kind of substituentselected from the group consisting of an amino group, an amide group, anether group, and a carboxyl group, and which has a total carbon numberof 10 to 200, the hydrogen atom and the hydrocarbon group being bondedto a carbon atom, R¹ and R² do not each represent a hydrogen atom at thesame time in a case where “p” represents 0, and R¹ to R⁴ do not eachrepresent a hydrogen atom at the same time in a case where “p”represents 1; and Y¹ and Y² each independently represent a hydrogenatom, a halogen atom, a functional group selected from the groupconsisting of an amino group, an amide group, a hydroxyl group, acarbonyl group, an aldehyde group, a carboxyl group, an ester group, andan ether group, or a hydrocarbon group which may have at least one kindof functional group selected from the group consisting of the abovefunctional groups and has a total carbon number of 1 to 30;

(2) A detergent-dispersant according to Item (1), in which: p in thegeneral formula (I) represents 1; and X¹, X², X³, and X⁴ in the generalformula (I) each independently represent “N” or “NH”;

(3) A detergent-dispersant according to Item (1), in which the generalformula (I) includes a heterocyclic skeleton derived from a compoundselected from the group consisting of pyridines, pyrroles, pyrimidines,pyrazoles, pyridazines, imidazoles, pyrazines, triazines, triazoles,tetrazoles, oxazoles, oxadiazoles, thiazoles, thiadiazoles, furans,dioxanes, pyrans, and thiophenes;

(4) A detergent-dispersant according to Item (1), in which theheterocyclic compound includes a boride thereof;

(5) An additive composition for a lubricant containing thedetergent-dispersant according to Item (1);

(6) A lubricant composition containing the detergent-dispersantaccording to Item (1); and

(7) A lubricant composition according to Item (6), which is a lubricantcomposition for an internal combustion engine.

Effects by the Invention

By using the lubricant composition containing the detergent-dispersantof the present invention, the heterocyclic compound exhibits excellenthigh temperature stability, high temperature detergency, basevalue-maintainable property, and fine particle-dispersibility in, forexample, a gasoline engine oil, a diesel engine oil, a two-cycle engineoil, and the like for an internal combustion engine.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention is described in detail.

A detergent-dispersant of the present invention is comprized aheterocyclic compound represented by the general formula (I).

In the general formula (I),

(1) in the case where “p” represents 0:

X¹, X², and X³ each independently represent “N” or “NH”, O, or “S”; “x”and “y” each independently represent an integer of 0 to 2, “v”represents an integer of 0 to 5, “n” and “m” each independentlyrepresent an integer of 0 to 3, and “x”, “y”, “n”, “m”, and “v” do noteach represent 0 at the same time; and R¹ and R² each independentlyrepresent a hydrogen atom or a hydrocarbon group which may have at leastone kind of substituent selected from the group consisting of an aminogroup, an amide group, an ether group, and a carboxyl group, and whichhas a total carbon number of 10 to 200, the hydrogen atom and thehydrocarbon group being bonded to a carbon atom, and R¹ and R² do noteach represent a hydrogen atom at the same time.

In the general formula (I),

(2) in the case where “p” represents 1:

X¹, X², X³, and X⁴ each independently represent “N” or “NH”, “O”, or“S”; “x” and “y” each independently represent an integer of 0 to 2, “u”and “r” each independently represent an integer of 0 to 4, “t” and “w”each independently represent an integer of 0 to 3, “v” represents aninteger of 0 to 3, “n” and “m” each independently represent an integerof 0 to 3, and “k” represents an integer of 0 to 3; and R¹ to R⁴ eachindependently represent a hydrogen atom or a hydrocarbon group which mayhave at least one kind of substituent selected from the group consistingof an amino group, an amide group, an ether group, and a carboxyl group,and has a total carbon number of 10 to 200, the hydrogen atom and thehydrocarbon group being bonded to a carbon atom, and R¹ to R⁴ do noteach represent a hydrogen atom at the same.

Y¹ and Y² each independently represent a hydrogen atom, a halogen atom,a functional group selected from the group consisting of an amino group,an amide group, a hydroxyl group, a carbonyl group, an aldehyde group, acarboxyl group, an ester group, and an ether group, or a hydrocarbongroup which may have at least one kind of functional group selected fromthe group consisting of the above functional groups and has a totalcarbon number of 1 to 30.

In the hydrocarbon group of the detergent-dispersant of the presentinvention, which is comprised the heterocyclic compound represented bythe general formula (I), when the carbon number is 10 or more, thesolubility with respect to a base oil for a lubricant is sufficient, andwhen the carbon number is 200 or less, the hydrocarbon group becomes acompound having excellent detergency and dispersibility and in addition,high temperature stability, base value-maintainable property, and thelike are ensured.

R¹ to R⁴ preferably represent a hydrogen atom or a hydrocarbon grouphaving a carbon number of 12 to 150. Specific examples thereof includehydrocarbon groups such as a dodecyl, dodecenyl, tetradecene,tetradecenyl, hexadecene, hexadecenyl, octadecyl, octadecenyl, oleyl,stearyl, isostearyl, decene trimer, or a polybutene group, each of whichmay be linear or branched.

The heterocyclic compound represented by the general formula (I) is, forexample, a reaction product obtained by allowing to react one of (a)which is a compound having pyridine, pyrrole, pyrimidine, pyrazole,pyridazine, imidazole, pyrazine, triazine, triazole, benzotriazole,tetrazole, oxazole, oxadiazole, thiazole, thiadiazole, furane, orthiophene as a basic skeleton, or derivatives thereof, the compound orthe derivatives forming the basic skeleton of a heterocyclic ring, withone of (b) which is a halogen compound having an alkyl group, an alkenylgroup, or a cycloalkyl group having a carbon number of 10 to 200, anamine compound, alcohols, an epoxy compound, or a compound having acarboxyl group, at a molar ratio (a):(b) of 1:5 to 5:1 and preferably1:2 to 2:1.

When the molar ratio (a):(b) is 1:5 or more to 5:1 or less, an activeingredient amount of the detergent-dispersant of the present inventionis prevented from becoming small, and the necessity of using a largeamount of the detergent-dispersant in order to exhibit high temperaturestability, high temperature detergency, and base value-maintainableproperty is prevented from occurring.

A reaction between (a) and (b) is performed at room temperature to 250°C. and preferably at 50 to 220° C. The reaction may be performed withouta catalyst or under the presence of the catalyst. Further, in performingthe reaction, there may be used a solvent, for example, an organicsolvent such as hexane, toluene, xylene, THF, or DMF.

In the heterocyclic compound represented by the general formula (I), thebasic skeleton of a heterocyclic ring is a saturated or unsaturatedcompound in which one ring has a total number of nitrogen atom and/oroxygen atom and/or sulfur atom of 1 to 4. Examples of the cycliccompound include pyridine, pyrrole, pyrimidine, pyrazole, pyridazine,imidazole, pyrazine, triazine, triazole, tetrazole, oxazole, oxadiazole,thiazole, thiadiazole, furane, thiophene, and derivatives thereof.Preferred are pyridine, pyrrole, pyrimidine, pyrazole, pyridazine,imidazole, pyrazine, triazole, tetrazole, oxadiazole, thiazole, andthiadiazole, and more preferred are pyridine, pyrimidine, pyrrole,pyrazole, imidazole, triazole, and derivatives thereof. Those may be themonocyclic compounds described above or polycyclic compounds such asindole, indazole, benzotriazole, benzoimidazole, purine, quinoline,isoquinoline, naphthyridine, carbazole, and naphthoimidazole. Further,examples of the cyclic compound may include a compound in which ahydrocarbon group or an amine, an amide, an alcohol, a ketone, analdehyde, a carboxylic acid, an ester, an ether, a halogen, and ahydrocarbon compound including those may be added to the heterocycliccompound as a functional group.

Examples of the functional group which may be added to the heterocycliccompound include a group such as methyl, ethyl, propyl, butyl, pentyl,hexyl, amine, amide, alcohol, methylcarboxy, ethylcarboxy, aldehyde,carboxylic acid, acetoxyl, propoxyl, butyroylxyl, halogen, ethyloxy,propyloxy, ethylamine, methylamine, dimethylamine, diethylamine,polyethylene polyamine, diethylene triamine, triethylene tetraamine,tetraethylene pentaamine, and aminoethyl piperazine.

Examples of compound (b) include bromine-based compounds such as2-decyl-1-bromotetradecane, 2-butyl-1-bromooctane,2-pentyl-1-bromononane, 2-hexyl-1-bromodecane, 2-heptyl-1-bromoundecane,2-octyl-1-bromododecane, 2-nonyl-1-bromotridecane,2,4-dioctyl-1-bromotetradecane, bromopolybutene, bromododecane,bromotetradecane, bromohexadecane, bromooctadecane, bromoeicosane,bromodocosane, bromotetracosane, bromoisostearyl, chlorine-basedcompounds such as 2-decyl-1-chlorotetradecane, 2-butyl-1-chlorooctane,2,4-dioctyl-1-chlorotetradecane chloropolybutane, chlorododecane, andchlorotetracosane; iodine-based compounds such as2-decyl-1-iodotetradecane, 2-butyl-1-iodooctane,2,4-dioctyl-1-iodotetradecane, iodopolybutene, iodododecane, andiodotetracosane; epoxy compounds such as 2-decyl-1,2-epoxytetradecane,2-butyl-1,2-epoxyoctane, 2,4-dioctyl-1,2-epoxytetradecane,polybuteneepoxide, 1,2-epoxydodecane, and 1,2-epoxytetracosane; aminecompounds such as 2-decyl-tetradecylamine, 2-butyl-octylamine,2,4-dioctyl-1-tetradecylamine, polybutenylamine, dodecylamine, andtetracosylamine; alcohols such as 2-decyl-tetradecyl alcohol,2-butyl-octyl alcohol, 2,4-dioctyl-1-tetradecyl alcohol, polybutenylalcohol, dodecyl alcohol, and tetracosyl alcohol; and compounds having acarboxyl group such as 2-decyl-tetradecanoic acid, 2-butyl-octanoicacid, 2,4-dioctyl-1-tetradecanoic acid, polybutenyl carboxylic acid,dodecanoic acid, and tetracosanic acid. One kind of those may be usedalone or two or more kinds thereof may be used as a mixture.

In the heterocyclic compound represented by the general formula (I), acyclic structure part in the case where “p” represents 0 or two cyclicstructure parts in the case where “p” represents 1 are derived from thecompound (a). At least one of R¹ to R⁴ is derived from the compound (b).

An additive composition for a lubricant can be obtained by mixing theheterocyclic compound represented by the general formula (I), which isobtained as described hereinabove and is the detergent-dispersant of thepresent invention, with various additives for lubricants. Further, alubricant composition of the present invention can be obtained by usingthe detergent-dispersant alone or by mixing the additive composition fora lubricant with a base oil for a lubricant.

In addition, a boride of a heterocyclic compound, which is oneembodiment of the detergent-dispersant of the present invention, is areaction product obtained by allowing to react the heterocyclic compoundobtained as described hereinabove with a boron-containing compound at amolar ratio of the heterocyclic compound to the boron-containingcompound of 1:0.01 to 1:10 and more preferably 1:0.05 to 1:5. Thereaction of the heterocyclic compound with the boron-containing compoundis performed at 50 to 250° C. and preferably at 100 to 200° C. Inperforming the reaction, there may be used a solvent such as an organicsolvent, e.g., a hydrocarbon oil. As the boron-containing compound,there may be used, for example, boron oxide, boron halide, boric acid,boric anhydride, and borate.

It should be noted that the boride of the heterocyclic compound obtainedfrom the reaction has a structure in which boric acid is added orsubstituted for hydrogen in “NH”, in the case where parts of X¹, X², X³,X⁴, R¹ to R⁴, Y¹, and Y² in the general formula (I) each independentlyrepresent “N”, “NH”, or an amino group.

Examples of the various additives for lubricants include the following(preferred content and more preferred content in the total amount of thelubricant composition containing the base oil for a lubricant describedlater are described in parentheses).

The examples thereof include viscosity index improving agents of apolymethacrylate base and the like (preferably 1 to 12, more preferably1 to 4% by mass), corrosion inhibitors of a benzotriazole base and thelike (preferably 0.01 to 3, more preferably 0.01 to 1.5% by mass),antioxidants of alkylated diphenylamine and the like (preferably 0.01 to5, more preferably 0.01 to 1.5% by mass), dispersants ofpolybutenylsuccinic imide and the like (preferably 0.1 to 10, morepreferably 0.1 to 5% by mass), fluidity improving agents for a lubricant(preferably 0.01 to 2, more preferably 0.01 to 1.5% by mass), rustinhibitors of an alkenylsuccinic ester base and the like (preferably0.01 to 6, more preferably 0.01 to 3% by mass), pour point depressantsof polymethacrylate and the like (preferably 0.01 to 1.5, morepreferably 0.01 to 0.5% by mass), defoaming agents (preferably 0.001 to0.1, more preferably 0.001 to 0.01% by mass), anti-wear agents of aphosphorous ester base and the like (preferably 0.001 to 5, morepreferably 0.001 to 1.5% by mass), seal swelling agents (preferably 0.1to 8, more preferably 0.1 to 4% by mass), and friction controllingagents of fatty acid amide and the like (preferably 0.01 to 3, morepreferably 0.01 to 1.5% by mass).

It should be noted that the detergent-dispersant of the presentinvention is used in a content of 0.01 to 15% by mass and preferably0.05 to 10% by mass with respect to the total amount of thedetergent-dispersant and the base oil for a lubricant. When the contentis 0.01% by mass or more, cleaning and dispersing effects can beexhibited, and when the content is 15% by mass or less, an increase inthe cost and a reduction in intrinsic characteristics endowed to thebase oil for a lubricant can be avoided.

The base oil for a lubricant is not particularly limited, and variousbase oils for a mineral oil-based lubricant and synthetic oil-basedlubricant can be used.

A specific example of the base oil for the mineral oil-based lubricantincludes a hydrocarbon oil produced by refining a lubricant fraction,which is obtained by distilling crude oil under atmospheric pressure andreduced pressure, by appropriately combined refining treatmentsincluding solvent deasphalting, solvent extraction, hydro-cracking,solvent dewaxing, catalytic dewaxing, hydrorefining, washing withsulfuric acid, and clay treatment.

Herein, all of lubricants such as a paraffin-based mineral oil, anaphthene-based mineral oil, and an aromatic mineral oil can be used asthe hydrocarbon oils.

Further, specific examples of a base oil for the synthetic oil-basedlubricant which may be used include phenyl ether-based synthetic oilssuch as polyphenyl ether; polyole fin-based synthetic oils such as polyα-olefin (for example, a polybutene, 1-octene oligomer, a 1-deceneoligomer, and hydrogenates thereof); benzene-based synthetic oils suchas alkylbenzene; naphthalene-based synthetic oils such asalkylnaphthalene; ester-based synthetic oils such as diesters (forexample, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyadipate, ditridecy adipate, and di-2-ethylhexyl sepacate) and polyolesters (for example, trimethylolpropane carpriate, trimethylolpropanepelargonate, pentaerythritol 2-ethyl hexanoate, and pentaerythritolpelargonate); glycol-based synthetic oils such as polyoxyalkyleneglycol; ether-based synthetic oils such as polyphenyl ether; andsilicone-based synthetic oils such as silicone fluorinated oil. One kindof those may be used alone or two or more kinds thereof may be used as amixture.

The product obtained by blending the detergent-dispersant of the presentinvention with a hydrocarbon oil, the lubricant fraction of a syntheticoil, or a mixture thereof can be used as a lubricant composition for aninternal combustion engine (e.g., lubricant composition for a dieselengine), a gear oil, a bearing oil, a transmission oil, a shock absorberoil, and an industrial lubricant.

The product obtained by blending the heterocyclic compound with ahydrocarbon fuel oil is remarkable in cleaning and dispersing effectsand can be used as a detergent for preventing a contaminant from beingattached to a carburetor of an internal combustion engine and removingthe attached matter.

EXAMPLES

Hereinafter, the present invention is described in further detail by wayof examples and comparative examples, but the present invention is notlimited to those examples.

Synthesis Example 1

Into a 500-ml flask there were charged 1.4 g (0.037 mol) of NaH (60%)and 20 ml of dimethylformamide (DMF). A solution in which 4.2 g (0.036mol) of benzoimidazole were dissolved in 30 ml of DMF was added dropwiseinto the mixture, followed by a reaction at room temperature for 30minutes. Subsequently, a solution in which 12.6 g (0.03 mol) of2-decyl-1-bromotetradecane were dissolved in 15 ml of toluene was addeddropwise into the reaction mixture, followed by a reaction at 100° C.for 7 hours. After the solvent has been distilled off, the residue wasdissolved in 300 ml of hexane and washed with water. The organic layerwas dried over magnesium sulfate and then hexane was distilled off. Theresidue was purified by a silica gel column chromatography, to therebyobtain 11.2 g of a heterocyclic compound, which was a target product.The structural formula of the heterocyclic compound is as follows. Inthe general formula (I), “p” represents 1, “n” represents 1, “y”represents 1, “u” represents 4, “m”, “w”, “v”, “k”, and “r” eachrepresent 0, X² and X³ each represent N, R¹ represents a2-decyltetradecyl group, R², R³, and R⁴ each represent a hydrogen atom,and Y¹ and Y² also each represent a hydrogen atom.

This heterocyclic compound is referred to as “Detergent-dispersant 1”.

Synthesis Example 2

A reaction was performed in the same manner as in Synthesis Example 1except that 3.1 g (0.036 mol) of 2-aminotetrazole were used instead ofbenzoimidazole, to thereby obtain 6.3 g of a heterocyclic compound,which was a target product. The structural formula of the heterocycliccompound is as follows. In the general formula (I), “m” represents 3,“v” represents 1, “x”, “n”, “p”, “u”, “r”, and “k” each represent 0, X¹and X³ each represent “N”, R¹ represents a 2-decyltetradecyl group, R²represents a hydrogen atom, and Y¹ represents an amino group.

This heterocyclic compound is referred to as “Detergent-dispersant 2”.

Synthesis Example 3

A reaction was performed in the same manner as in Synthesis Example 1except that 2.5 g (0.036 mol) of imidazole were used instead ofbenzoimidazole, to thereby obtain 8.5 g of a heterocyclic compound,which was a target product. The structural formula of the heterocycliccompound is as follows. In the general formula (I), “m” represents 1,“v” represents 2, “x” represents 1, “n”, “p”, “u”, “r”, and “k” eachrepresent 0, X¹ and X³ each represent “N”, R¹ represents a2-decyltetradecyl group, R² represents a hydrogen atom, and Y¹represents a hydrogen atom. This heterocyclic compound is referred to as“Detergent-dispersant 3”.

Synthesis Example 4

A reaction was performed in the same manner as in Synthesis Example 1except that 3.1 g (0.036 mol) of 2-aminobenzoimidazole were used insteadof benzoimidazole, to thereby obtain 9.3 g of a heterocyclic compound,which was a target product. The structural formula of the heterocycliccompound is as follows. In the general formula (I), “p” represents 1,“n” represents 1, “y” represents 1, “u” represents 4, “m”, “w”, “v”,“k”, and “r” each represent 0, X² and X³ each represent “N”, R¹represents a 2-decyltetradecyl group, R², R³, and R⁴ each represent ahydrogen atom, Y¹ represents an amino group, and Y² represents ahydrogen atom.

This heterocyclic compound is referred to as “Detergent-dispersant 4”.

Synthesis Example 5

A reaction was performed in the same manner as in Synthesis Example 1except that 3.1 g (0.036 mol) of aminopyrazine were used instead ofbenzoimidazole, to thereby obtain 4.1 g of a heterocyclic compound,which was a target product. The structural formula of the heterocycliccompound is as follows. In the general formula (I), “p” represents 0,“m” represents 1, “v” represents 2, “x” represents 2, “n”, “u”, “r”, and“k” each represent 0, X¹ and X³ each represent “N”, R¹ represents a1-amino-2-decyltetradecyl group, R² represents a hydrogen atom, and Y¹represents a hydrogen atom.

This heterocyclic compound is referred to as “Detergent-dispersant 5”.

Synthesis Example 6

Into a 1-l flask there were charged 7.4 g (0.073 mol) ofdiisopropylamine (iPr₂NH) and 100 ml of tetrahydrofuran (THF). 44 ml ofnormal butyl lithium (nBuLi) (1.67 M hexane solution, 0.073 mol) wereadded dropwise into the mixture at −30° C., followed by stirring at thesame temperature for 30 minutes. Subsequently, a solution of 5.1 g(0.055 mol) of γ-picoline in THF (80 ml) was added to the resultant,followed by stirring at −10° C. for 1 hour and 15 minutes.

Subsequently, a solution of 15.0 g (0.036 mol) of2-decyl-1-bromotetradecane in THF (80 ml) was added dropwise into theresultant, and the mixture was allowed to react at room temperature for1 hour and then at 40° C. for 4 hours.

After 300 ml of a saturated ammonium chloride aqueous solution wereadded to the reaction mixture, an organic layer was extracted from themixture with 500 ml of hexane, and the organic layer was dried withmagnesium sulfate. After the solvent has been distilled off, the residuewas purified by a silica gel column chromatography, to thereby obtain5.6 g of a heterocyclic compound, which was a target product. Thestructural formula of the heterocyclic compound is as follows. In thegeneral formula (I), “p” represents 0, “v” represents 5, “m”, “n”, “u”,“r”, and “k” each represent 0, X³ represents “N”, R¹ represents a3-decylpentadecyl group, R² represents a hydrogen atom, and Y¹represents a hydrogen atom. This heterocyclic compound is referred to as“Detergent-dispersant 6”.

Synthesis Example 7

A reaction was performed in the same manner as in Synthesis Example 6except that 5.1 g (0.055 mol) of α-picoline were used instead ofγ-picoline, to thereby obtain 5.6 g of a heterocyclic compound, whichwas a target product. The structural formula of the heterocycliccompound is as follows. In the general formula (I), “p” represents 0,“v” represents 5, “m”, “n”, “u”, “r”, and “k” each represent 0, X³represents “N”, R¹ represents a 3-decylpentadecyl group, R² represents ahydrogen atom, and Y¹ represents a hydrogen atom.

This heterocyclic compound is referred to as “Detergent-dispersant 7”.

Synthesis Example 8

Into a 300-ml four-neck flask there were charged 93 g (0.22 mol) of(2-decyl-1-tetradecanyl)-2-aminotetrazole synthesized in SynthesisExample 2 and 6.3 g (0.102 mol) of boric acid, and the mixture wasallowed to react while stirring under nitrogen stream at 150° C. for 4hours. The generated water was distilled off under reduced pressure at150° C. and the reactant was filtered, to thereby obtain 96 g of aboride of a heterocyclic compound, which was a target product. Thestructural formula of the boride is as follows. In the general formula(I), “m” represents 3, “v” represents 1, “x”, “n”, “p”, “u”, “r”, and“k” each represent 0, X¹ and X³ each represent “N”, R¹ represents a2-decyltetradecyl group, R² represents a hydrogen atom, and Y¹represents a (dihydroxyboranyl) amino group.

This boride is referred to as “Detergent-dispersant 8”.

Synthesis Example 9

Into a 300-ml four-neck flask there were charged 105 g (0.22 mol) of1-(2-decyl-1-tetradecanyl)-2-aminobenzoimidazole synthesized inSynthesis Example 4 and 6.3 g (0.102 mol) of boric acid, and the mixturewas allowed to react under nitrogen stream at 150° C. for 4 hours.

The generated water was distilled off under reduced pressure at 150° C.and the reactant was filtered, to thereby obtain 108 g of a boride of aheterocyclic compound, which was a target product. The structuralformula of the boride is as follows. In the general formula (I), “p”represents 1, “n” represents 1, “y” represents 1, u represents 4, m, w,v, k, and r each represent 0, X² and X³ each represent “N”, R¹represents a 2-decyltetradecyl group, R², R³, and R⁴ each represent ahydrogen atom, Y¹ represents a (dihydroxyboranyl) amino group, and Y²represents a hydrogen atom.

This boride is referred to as “Detergent-dispersant 9”.

Comparative Synthesis Example 1

Into a 2-liter autoclave there were charged 1,100 g of polybutene (Mw:987), 6.4 g (0.021 mol) of cetyl bromide, and 115 g (1.2 mol) of maleicanhydride, and the mixture was subjected to nitrogen substitution andallowed to react at 240° C. for 5 hours. The temperature was lowered to215° C., and unreacted maleic anhydride and cetyl bromide were distilledoff under reduced pressure. The temperature was lowered to 140° C., andthe resultant was filtered. The yield of the thus obtainedpolybutenylsuccinic anhydride was 1,100 g. Into a 2-liter separableflask there were charged 500 g of the obtained polybutenylsuccinicanhydride, 64 g (0.34 mol) of tetraethylenepentamine (TEPA), and 300 gof a mineral oil of 150 neutral fraction, and the mixture was allowed toreact under nitrogen stream at 150° C. for 2 hours. The temperature wasraised to 200° C., and unreacted TEPA and generated water were distilledoff under reduced pressure. The temperature was lowered to 140° C., andthe resultant was filtered. Thus, 790 g of a comparative heterocycliccompound (polybutenylsuccinicimide) were obtained. The structuralformula of the comparative heterocyclic compound is as follows. In thegeneral formula (I), Y¹ becomes an oxygen double bond. Accordingly, thecomparative heterocyclic compound is not included in the scope of thedetergent-dispersant of the present invention.

This comparative heterocyclic compound is referred to as “ComparativeDetergent-dispersant 1”.

Comparative Synthesis Example 2

A reaction was performed in the same manner as in Comparative SynthesisExample 1, except that 915 g of polybutene (Mw: 800) were used insteadof polybutene (Mw: 987). The yield of the thus obtainedpolybutenylsuccinic anhydride was 940 g. Subsequently, a reaction wasperformed in the same manner as in Comparative Synthesis Example 1 byusing 500 g of the obtained polybutenylsuccinic anhydride, 76 g (0.40mol) of tetraethylenepentamine (TEPA), and 300 g of a mineral oil of 150neutral fraction. Thus, 810 g of a comparative heterocyclic compound(polybutenylsuccinic imide) were obtained. The structural formula of thecomparative heterocyclic compound is as follows. In the general formula(I), Y¹ becomes an oxygen double bond. Accordingly, the comparativeheterocyclic compound is not included in the scope of thedetergent-dispersant of the present invention.

This comparative heterocyclic compound is referred to as “ComparativeDetergent-dispersant 2”.

Comparative Synthesis Example 3

A reaction was performed in the same manner as in Comparative SynthesisExample 1, except that 890 g of polybutene (Mw: 445), 11 g (0.036 mol)of cetyl bromide, and 397 g (2.1 mol) of maleic anhydride were usedinstead of polybutene (Mw: 987). The yield of the thus obtainedpolybutenylsuccinic anhydride was 990 g. Subsequently, a reaction wasperformed in the same manner as in Comparative Synthesis Example 1 byusing 500 g of the obtained polybutenylsuccinic anhydride, 88 g (0.60mol) of triethylenetetramine (TETA), and 300 g of a mineral oil of 150neutral fraction. Thus, 820 g of a comparative heterocyclic compound(polybutenylsuccinicimide) were obtained. The structural formula of thecomparative heterocyclic compound is as follows. In the general formula(I), Y¹ becomes an oxygen double bond. Accordingly, the comparativeheterocyclic compound is not included in the scope of thedetergent-dispersant of the present invention.

This comparative heterocyclic compound is referred to as “ComparativeDetergent-dispersant 3”.

Examples 1 to 9 and Comparative Examples 1 to 3

Lubricant compositions were each prepared by adding, to 90 parts by massof a mineral oil of 500 neutral fraction, 10 parts by mass of one of“Detergent-dispersants 1 to 9” obtained in Synthesis Examples 1 to 9 and“Comparative Detergent-dispersants 1 to 3” obtained in ComparativeSynthesis Examples 1 to 3.

The performances of those lubricant compositions were evaluated by a hottube test under the following conditions. Table 1 shows the results.

[Hot Tube Test]

The lubricant composition and air were allowed to flow continuously at arate of 0.3 ml/hr and a rate of 10 ml/min, respectively, for 16 hoursthrough a glass tube which is kept at 250° C. and has an inner diameterof 2 mm. The lacquer adhered to the test tube was compared with a colorsample and was evaluated into 11 grades, from 10 points in the case ofcolorless to 0 point in the case of black. At the same time, the mass ofthe lacquer adhered to the test tube was measured. The results show thatthe larger the grade becomes or the smaller the amount of the adheredlacquer becomes, the higher the performance of the lubricant compositionis. The test was performed in accordance with JPI-5S-55-99.

[Base Value-Maintainable Property Test]

The test oil obtained after the hot tube test described above wascollected, and the base value was determined by a hydrochloric acidmethod in accordance with JIS K2501. The base value-maintainableproperty was evaluated by comparing a base value after the test(residual base value) to a base value before the test (initial basevalue) and expressing the result as a residual base value ratio (%)[residual base value ratio (%)=(residual base value/initial basevalue)×100]. The results show that the higher the residual base valueratio becomes, the higher the performance of the base value-maintainableproperty is.

[Table 1]

TABLE 1 Mass of adhered Initial Residual base Used lacquer base valueratio detergent-dispersant Grade (mg) value (%) Example 1Detergent-dispersant 1 10 0 0.42 223 Example 2 Detergent-dispersant 2 81.4 0.15 154 Example 3 Detergent-dispersant 3 9 2.4 8.42 57 Example 4Detergent-dispersant 4 10 0 11.1 60 Example 5 Detergent-dispersant 5 62.6 1.3 21 Example 6 Detergent-dispersant 6 9 3.4 0.24 361 Example 7Detergent-dispersant 7 8 5.6 0.14 340 Example 8 Detergent-dispersant 810 0 0.13 128 Example 9 Detergent-dispersant 9 10 0 10.0 72 ComparativeComparative 0 45 7.7 2 Example 1 Detergent-dispersant 1 ComparativeComparative 0 48 8.5 1 Example 2 Detergent-dispersant 2 ComparativeComparative 0 57 9.8 2 Example 3 Detergent-dispersant 3

INDUSTRIAL APPLICABILITY

The product in which the detergent-dispersant of the present inventionis blended in a mineral oil-based hydrocarbon oil, a synthetic lubricantbase oil, or the mixture thereof has improved detergency anddispersibility and exerts excellent fuel consumption reduction effect inan internal combustion engine and a transmission engine of a drivingsystem. In addition, the product is ashless, and hence is suitable as anenvironment-responsive detergent-dispersant.

1. A detergent-dispersant comprising a heterocyclic compound which isrepresented by the following general formula (I), and which may have adouble bond in a cyclic moiety:

where: X¹, X², X³, and X⁴ each independently represent “N” or “NH”, “O”,or “S”; “p” represents 0 or 1, “x” and “y” each independently representan integer of 0 to 2, “u” and “r” each independently represent aninteger of 0 to 4, “t” and “w” each independently represent an integerof 0 to 3, “v” represents an integer of 0 to 5 in a case where “p”represents 0 and “v” represents an integer of 0 to 3 in a case where “p”represents 1, “n” and “m” each independently represent an integer of 0to 3, “k” represents an integer of 0 to 3, and “x”, “y”, “n”, “m”, and“v” do not each represent 0 at the same time in a case where “p”represents 0; R¹ to R⁴ each independently represent a hydrogen atom or ahydrocarbon group which may have at least one kind of substituentselected from the group consisting of an amino group, an amide group, anether group, and a carboxyl group, and which has a total carbon numberof 10 to 200, the hydrogen atom and the hydrocarbon group being bondedto a carbon atom, R¹ and R² do not each represent a hydrogen atom at thesame time in a case where “p” represents 0, and R¹ to R⁴ do not eachrepresent a hydrogen atom at the same time in a case where “p”represents 1; and Y¹ and Y² each independently represent a hydrogenatom, a halogen atom, a functional group selected from the groupconsisting of an amino group, an amide group, a hydroxyl group, acarbonyl group, an aldehyde group, a carboxyl group, an ester group, andan ether group, or a hydrocarbon group which may have at least one kindof functional group selected from the group consisting of the abovefunctional groups and has a total carbon number of 1 to
 30. 2. Thedetergent-dispersant according to claim 1, wherein: “p” in the generalformula (I) represents 1; and X¹, X², X³, and X⁴ in the general formula(I) each independently represent “N” or “NH”.
 3. Thedetergent-dispersant according to claim 1, wherein the general formula(I) comprises a heterocyclic skeleton derived from a compound selectedfrom the group consisting of pyridines, pyrroles, pyrimidines,pyrazoles, pyridazines, imidazoles, pyrazines, triazines, triazoles,tetrazoles, oxazoles, oxadiazoles, thiazoles, thiadiazoles, furans,dioxanes, pyrans, and thiophenes.
 4. The detergent-dispersant accordingto claim 1, wherein the heterocyclic compound comprises a boridethereof.
 5. An additive composition for a lubricant containing thedetergent-dispersant according to claim
 1. 6. A lubricant compositioncontaining the detergent-dispersant according to claim
 1. 7. Thelubricant composition according to claim 6, which is a lubricantcomposition for an internal combustion engine.